JPH0360413A - Production of carbon material - Google Patents
Production of carbon materialInfo
- Publication number
- JPH0360413A JPH0360413A JP1192591A JP19259189A JPH0360413A JP H0360413 A JPH0360413 A JP H0360413A JP 1192591 A JP1192591 A JP 1192591A JP 19259189 A JP19259189 A JP 19259189A JP H0360413 A JPH0360413 A JP H0360413A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- coating
- coating film
- ceramics
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 13
- 239000012808 vapor phase Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 39
- 238000000576 coating method Methods 0.000 abstract description 39
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000005336 cracking Methods 0.000 abstract description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 2
- 238000000151 deposition Methods 0.000 description 16
- 230000008021 deposition Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000011295 pitch Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000003763 carbonization Methods 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 8
- 239000004917 carbon fiber Substances 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001513 hot isostatic pressing Methods 0.000 description 3
- 239000011301 petroleum pitch Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002296 pyrolytic carbon Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000011337 anisotropic pitch Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- UDWPONKAYSRBTJ-UHFFFAOYSA-N [He].[N] Chemical compound [He].[N] UDWPONKAYSRBTJ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000011304 carbon pitch Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00405—Materials with a gradually increasing or decreasing concentration of ingredients or property from one layer to another
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は耐酸化性を有する炭素材料の製造法に関する。[Detailed description of the invention] Industrial applications The present invention relates to a method for producing a carbon material having oxidation resistance.
従来の技 および解決しようとする課題炭素／炭素複合
材料は、不活性雰囲気下では１０００℃以上の高温にお
いても高強度、高弾性率を維持し、かつ熱膨張率が小さ
い等の性質を有する材料であり、航空宇市機器の部品、
ブレーキ、炉材等への利用が期待されている。Conventional techniques and issues to be solved Carbon/carbon composite materials are materials that maintain high strength and high modulus of elasticity even at high temperatures of 1000°C or higher in an inert atmosphere, and have low coefficient of thermal expansion. and Aerospace equipment parts,
It is expected to be used for brakes, furnace materials, etc.
しかしながら空気中では５００℃程度から酸化消耗を受
ける欠点がある。However, it has the disadvantage that it is subject to oxidative consumption from about 500°C in air.
このため炭素／炭素複合材料の表面にセラミックスの被
膜を付与することにより耐酸化性を改良すｇ試みが行わ
れているが、基材となる炭素／炭素複合材料とセラミッ
クスの熱膨張の度合が異なるため、その界面における剥
離あるいは被膜のクラックなどが発生し、本来の機能を
十分に発揮するに至っていないのが現状である。For this reason, attempts have been made to improve the oxidation resistance by applying a ceramic coating to the surface of carbon/carbon composite materials, but the degree of thermal expansion between the base carbon/carbon composite material and the ceramics As a result, peeling or cracking of the coating occurs at the interface, and the current situation is that the original function is not fully demonstrated.
本発明者らは、炭素／炭素複合材料の耐酸化性を改良す
る方法について研究した結果、炭素１ｉ１ｉ１０〜７０
ＶＯＬ％および炭Ｔ：質マトリックス５〜９０ＶＯＬ％
から構成され、かつ開孔空隙率が１０〜５５％である炭
素／炭素複合材料の開孔空隙部に気相分解により炭素お
よび／またはセラミックスを沈積充填し、続いてこの充
填物の表面に気相分解によりセラミックスまたはセラミ
ックスおよび炭素の再考を沈積被覆することを特徴とす
る耐酸化性を有する炭素／炭素複合材籾の製造法を見い
だし、特願昭６３−７６００６号として出願した。As a result of research on methods for improving the oxidation resistance of carbon/carbon composite materials, the present inventors found that carbon 1i1i10-70
VOL% and charcoal T: quality matrix 5-90VOL%
Carbon and/or ceramics are deposited and filled into the open pores of a carbon/carbon composite material made of A method for producing carbon/carbon composite rice grains having oxidation resistance characterized by coating ceramics or a reconsideration of ceramics and carbon by phase decomposition was discovered and filed as Japanese Patent Application No. 76006/1983.
本発明者らは、さらに優れた耐酸化性を有する炭素材料
の製造法について鋭意研究を重ねた結果、本発明の完成
に至った。The present inventors have completed the present invention as a result of intensive research into a method for producing a carbon material having even better oxidation resistance.
すなわち本発明は、炭素／炭素複合材料の表面に、主と
して炭素よりなる第１被膜を気相分解により形成させ、
ついでセラミックスあるいはセラミックスと炭素の再考
よりなる第２被膜を気相分解により形成させ、かつ該第
１被膜内において炭素の熱物性あるいは機械物性の少な
（ともひとつを連続的にあるいは非連続的に変化させて
いることを特徴とする炭素材料の製造法に関する。That is, the present invention forms a first film mainly composed of carbon on the surface of a carbon/carbon composite material by vapor phase decomposition,
Next, a second coating made of ceramics or a reconsideration of ceramics and carbon is formed by vapor phase decomposition, and within the first coating, the thermophysical properties or mechanical properties of carbon are changed continuously or discontinuously. The present invention relates to a method for producing a carbon material, characterized in that:
以下に本発明を詳述する。The present invention will be explained in detail below.
本発明の炭素材料の基材となる炭素／炭素複合材料とは
、炭素＆ａ維と炭素質マトリックス等から構成される材
料をいう。The carbon/carbon composite material serving as the base material of the carbon material of the present invention refers to a material composed of carbon & a fibers, a carbonaceous matrix, and the like.
炭素ｔａＩ＆の割合は通常１０〜７０ｖｏ１％、好まし
くは２０〜６０ｖｏ１％である。The proportion of carbon taI& is usually 10 to 70 vol%, preferably 20 to 60 vol%.
上記の炭素／炭素複合材料を構成する炭素ｍ維としては
、ピッチ系、ポリアクリロニトリル系あるいはレーヨン
系等の種々の炭素ｍ維を用いることができ、特にピッチ
系炭素繊維が、耐酸化性を高め易く、好適である。As the carbon fibers constituting the above carbon/carbon composite material, various carbon fibers such as pitch-based, polyacrylonitrile-based, or rayon-based carbon fibers can be used. In particular, pitch-based carbon fibers have improved oxidation resistance. Easy and suitable.
前記炭素繊維は、通常５００〜２５０００本の繊維束と
して用いる。The carbon fibers are usually used in the form of a fiber bundle of 500 to 25,000 fibers.
さらに、一方向積層物、２次元織物あるいはその積層物
、３次元織物、マット状威形物、フェルト状成型物など
炭素繊維を２次元あるいは３次元の成形体としたものを
用いてもよく、特に、３次元織物が好ましい。Furthermore, two-dimensional or three-dimensional molded bodies of carbon fibers such as unidirectional laminates, two-dimensional fabrics or their laminates, three-dimensional fabrics, mat-like objects, and felt-like molded objects may also be used. In particular, three-dimensional fabrics are preferred.
炭素質マトリックスとしては、例えば、炭素質ピッチ、
フェノール樹脂、フランＩａ！ＩＩＩなどの炭化により
得られるもの、あいろは炭化水素の気相熱分解によるも
のむどが挙げられ、特に炭素質ピッチの炭化により得ら
れろものが好適である。Examples of the carbonaceous matrix include carbonaceous pitch,
Phenolic resin, Furan Ia! Examples include those obtained by carbonization such as III, and those obtained by vapor phase thermal decomposition of blue hydrocarbons, and those obtained by carbonization of carbonaceous pitch are particularly preferred.
上記の炭素質ピッチとしては、石炭系あるいは石油系の
ピッチが使用でき、特に軟化点が１００〜４００℃、好
ましくは１５０〜３５０℃であるピッチが望ましい。As the above-mentioned carbonaceous pitch, coal-based or petroleum-based pitch can be used, and pitch having a softening point of 100 to 400°C, preferably 150 to 350°C is particularly desirable.
さらに、上記の炭素質ピッチとしては、光学的に等方性
のピッチあるいは異方性のピッチを、単独または混合し
て使用でき、特に好ましくは光学異方性相の含有量が６
０〜１０［１％、最も好ましくは８０−１００％である
光学異方性ピッチの使用が望ましい。Further, as the above-mentioned carbonaceous pitch, optically isotropic pitch or anisotropic pitch can be used alone or in combination, and it is particularly preferable that the content of the optically anisotropic phase is 6.
It is desirable to use an optically anisotropic pitch of 0-10[1%, most preferably 80-100%.
本発明の基材となる炭素／炭素複合材料の製造法は特に
限定されず、公知の方法が用いられろ。The method for producing the carbon/carbon composite material that is the base material of the present invention is not particularly limited, and any known method may be used.
例えば、炭素質ピッチ、フェノール樹脂、フラン樹脂な
どを炭素繊維の織物あるいは成型物などに含浸した後、
常圧下、加圧下あるいはプレス下で炭化して得られろ。For example, after impregnating a carbon fiber fabric or molded product with carbon pitch, phenolic resin, furan resin, etc.
It can be obtained by carbonization under normal pressure, pressure, or press.
含浸は、炭素質ピッチなどを真空下で加熱、溶融するこ
とにより達成される。Impregnation is achieved by heating and melting carbonaceous pitch or the like under vacuum.
常圧下の炭化は、不活性ガス雰囲気下４００〜２０００
℃において実施することができる。また、加圧下の炭化
は、不活性ガスにより５０〜１００００ｋｇ／ｅ＋／に
等方加圧し、４００〜２０００℃において実施すること
ができる。また、プレス下の炭化は、ホットプレスなど
により１０〜５００ｋｇ／ｃＩｌの一軸加圧下、４００
〜２０００℃において実施することができる。Carbonization under normal pressure is 400 to 2000 in an inert gas atmosphere.
It can be carried out at ℃. Moreover, carbonization under pressure can be carried out at 400 to 2000° C. by isostatically pressurizing the material to 50 to 10,000 kg/e+/ with an inert gas. In addition, carbonization under press is performed under uniaxial pressure of 10 to 500 kg/cIl using a hot press, etc.
It can be carried out at a temperature of -2000°C.
また、ＨＩＰ （熱間静水圧加圧）装置を用いて炭化を
行うこともできる。Carbonization can also be carried out using a HIP (hot isostatic pressing) device.
ＨＩＰ装置におけろ加圧熱処理の条件は、不活性ガスに
よりＳｏ〜１００００ｋｇ／ｃｄ、好ましくは２００〜
２０００ｋｇ／ａｄに加圧し、１００〜３０００℃、好
ましくは４００〜２０００℃において実施することが出
来る。圧媒ガスとしては、アルゴン、窒素ヘリウムなど
の不活性ガスが使用出来る。加圧炭化に続く常圧下の炭
化あるいは黒鉛化は、不活性ガス雰囲気下４００〜３０
００℃において実施することが出来ろ。The conditions for pressure heat treatment in the HIP device are So~10000kg/cd, preferably 200~100kg/cd using an inert gas.
It can be carried out at a pressure of 2000 kg/ad and at a temperature of 100 to 3000°C, preferably 400 to 2000°C. As the pressure medium gas, inert gas such as argon, nitrogen helium, etc. can be used. Carbonization or graphitization under normal pressure following pressure carbonization is performed under an inert gas atmosphere at a temperature of 400 to 30
It can be carried out at 00°C.
本発明では、上記の方法により製造された炭素／炭素複
合材料の表面に、まず主として炭素より成る第１被膜を
気相分解法により形威し、かつ該第１被膜内において炭
素の熱物性あるいは機械物性の少なくともひとつを連続
的又は非連続的に変化させる。In the present invention, a first film mainly composed of carbon is first formed on the surface of the carbon/carbon composite material produced by the above method by a vapor phase decomposition method, and the thermophysical properties of carbon are At least one mechanical property is changed continuously or discontinuously.
ここで、上記熱物性とは、熱膨張係数あるいは熱伝導率
などを示し、熱物性を変化させるとは好ましくは熱膨張
係数を変化させろことをいう。Here, the above-mentioned thermal physical properties refer to the coefficient of thermal expansion or thermal conductivity, and changing the thermal physical properties preferably means changing the coefficient of thermal expansion.
このとき第１被膜の中で、炭素／炭素複合材料の表面付
近、すなわち第１被膜の最内層の熱膨張係数が第２被膜
付近、すなわち第１被膜の最外層の炭素の熱膨張係数よ
り小さいことが好ましい。具体的には、第１被膜の中で
最内層から最外層にかけて炭素の熱膨張係数が連続的又
は非連続的に大きくなっていることが望ましい。At this time, in the first coating, the coefficient of thermal expansion near the surface of the carbon/carbon composite material, that is, the innermost layer of the first coating is smaller than the coefficient of thermal expansion of carbon near the second coating, that is, the outermost layer of the first coating. It is preferable. Specifically, it is desirable that the coefficient of thermal expansion of carbon increases continuously or discontinuously from the innermost layer to the outermost layer in the first coating.
また、上記機械物性とは、ヤング率、強度、破断伸度な
どを示し、機械物性を変化させろとは好ましくはヤング
率を変化させることをいう。Further, the above-mentioned mechanical properties refer to Young's modulus, strength, elongation at break, etc., and changing mechanical properties preferably means changing Young's modulus.
このとき第１被膜の中で、炭素／炭素複合材料の表面付
近、すなわち第１被膜の最内層の炭素のヤング率が第２
被膜付近、すなわち第１被膜の最外層の炭素のヤング率
より大きい方が好ましい。At this time, in the first coating, the Young's modulus of carbon near the surface of the carbon/carbon composite material, that is, the innermost layer of the first coating, is the second.
It is preferable that the Young's modulus is larger than the Young's modulus of carbon near the coating, that is, in the outermost layer of the first coating.
具体的には、第１被膜の中で最内層から最外層にかけて
炭素のヤング率が連続的又は非連続的に小さくなってい
ることが望ましい。Specifically, it is desirable that the Young's modulus of carbon decreases continuously or discontinuously from the innermost layer to the outermost layer in the first coating.
そして上記のように、炭素よりなる第１被膜内において
これらの熱物性あるいは機械物性の少なくともひとつを
変化させろためには、熱分解炭素の構造あるいは組織を
変化させることによって達成できる。ここでいう熱分解
炭素のＨＩｔ造とは例えばＸ線回折、高分解能電子顕微
鏡あるいはラマンスペクトルなどによＩＩＩ識別できる
ような結晶レベルの構造をさす。As described above, changing at least one of these thermophysical properties or mechanical properties within the first coating made of carbon can be achieved by changing the structure or organization of the pyrolytic carbon. Here, the HIt structure of pyrolytic carbon refers to a crystal-level structure that can be identified by, for example, X-ray diffraction, high-resolution electron microscopy, or Raman spectroscopy.
また熱分解炭素の組織とは、例えば光学顕黴鑓あるいは
走査型電子［徴鏡において識別できるようなミクロンオ
ーダーの微細組織、配向などをさす。Furthermore, the structure of pyrolytic carbon refers to, for example, a fine structure and orientation on the micron order that can be discerned using an optical microscope or a scanning electron microscope.
本発明の第１被膜の製造法について以下に詳述する。The method for producing the first film of the present invention will be described in detail below.
本発明の第１被膜は気相分解法により形成されるが、気
相分解により主として炭素よりなるものを沈積する方法
は、通常ＣＶＤ （Ｃｈｅｍｉｃａ！ Ｖａｐｏｒ Ｄ
ｅｐｏｓｉｔｉｏｎ）と呼ばれて、具体的には熱ＣＶＤ
、プラズマＣＶＤ等が挙げられる。The first coating of the present invention is formed by a vapor phase decomposition method, but the method of depositing a material mainly composed of carbon by vapor phase decomposition is usually CVD (Chemica! Vapor D).
specifically called thermal CVD
, plasma CVD, and the like.
第１被膜を気相分解法、いわゆるＣＶＤ法による炭素の
沈積により生成させろ場合、熱分解ガスとしては、炭化
水素、好ましくは炭素数１〜６の炭化水素、具体的には
、メタン、天然ガス、プロパン、ブタン、ベンゼン、ア
セチレン等が用いられる。When the first film is produced by carbon deposition using a vapor phase decomposition method, so-called CVD method, the pyrolysis gas is a hydrocarbon, preferably a hydrocarbon having 1 to 6 carbon atoms, specifically, methane, natural gas, etc. , propane, butane, benzene, acetylene, etc. are used.
また、これらのガス中に、希釈のためにＮ、Ａｒ、 ）
ｌｓ。In addition, these gases contain N, Ar, ) for dilution.
ls.
Ｎｅ、 Ｋｒ、 Ｘｅ、 Ｒｎ等の不活性ガス、あるい
は水素を混合するとともできる。It can also be produced by mixing inert gases such as Ne, Kr, Xe, and Rn, or hydrogen.
熱分解ガスの供給速度は、反応に用いろ炉の大きさある
いは構造等により適宜決定される。The supply rate of the pyrolysis gas is appropriately determined depending on the size or structure of the filter furnace used for the reaction.
第１被膜内の炭素の熱物性あるいは機械物性の少なくと
も１つを連続的または非連続的に変化させるには、熱分
解条件のうち、例えば温度、圧力、熱分解ガス供給速度
、原料の希釈比の少なくとも１つを、連続的または非連
続的に変化させることにより達成できろ。In order to continuously or discontinuously change at least one of the thermophysical properties or mechanical properties of the carbon in the first coating, the thermal decomposition conditions such as temperature, pressure, pyrolysis gas supply rate, dilution ratio of the raw material, etc. This can be achieved by continuously or discontinuously changing at least one of the following.
このとき、第１被膜の沈積開始時には、異方性の高い炭
素を生成させ、炭素の沈積の進行とともに、沈積炭素の
異方性を、連続的もしくは非連続的に低下させ、炭素の
沈積終了時付近では異方性の低い炭素もしくは等方的な
炭素とする。At this time, at the start of deposition of the first film, highly anisotropic carbon is generated, and as the carbon deposition progresses, the anisotropy of the deposited carbon is reduced continuously or discontinuously, and the carbon deposition is completed. Carbon with low anisotropy or isotropic carbon is used around the time.
ここで、異方性の高い炭素とは通常、沈積平面上のａ軸
方向の熱膨張係数が、−１，Ｘ１０’〜２Ｘ１．ｏ
（１／℃）のものをいう。Here, highly anisotropic carbon usually has a thermal expansion coefficient in the a-axis direction on the deposition plane of -1.X10' to 2X1. o
(1/℃).
また、異方性の低い炭素もしくは等方的な炭素とは、熱
膨張係数が、２．５Ｘ１０ 〜５Ｘ１０ （１／’Ｃ
）のものをいう。In addition, carbon with low anisotropy or isotropic carbon has a thermal expansion coefficient of 2.5X10 to 5X10 (1/'C
).
具体的には、異方性の高い炭素を生成するには、前記の
気相分解法の条件を満たし、かつ温度が通常１０００〜
２５００℃、好ましくは１１００〜２０００℃、さらに
より好ましくは１１００〜１６００℃であることが望ま
しく、同時に圧力が０１〜１００１００ｎ、好ましくは
０．１〜５０ ｒａｌ（ｇ、さらにより好ましくは０．
１〜３０ ｍＨｇであることが望ましい。Specifically, in order to generate carbon with high anisotropy, the conditions for the gas phase decomposition method described above must be met, and the temperature is usually 1,000 to 1,000 ℃.
It is desirable that the temperature is 2500°C, preferably 1100-2000°C, even more preferably 1100-1600°C, and at the same time the pressure is 01-100100n, preferably 0.1-50 ral (g, even more preferably 0.
It is desirable that it is 1-30 mHg.
ついで、生成する炭素の異方性を連続的もしくは非連続
的に低下させるためには、圧力を上昇させる方法および
藁度を下げる方法のうちのいずれか一方を用いろことに
より行うことができ、特に再考を変化させる方法が好適
である。Next, in order to continuously or discontinuously reduce the anisotropy of the generated carbon, it can be done by using either a method of increasing the pressure or a method of decreasing the straw content, In particular, a method of changing reconsideration is suitable.
このとき、炭素の沈積開始以降沈積終了時の条件は、圧
力が沈積開始圧力以上、７６０ｍｍ Ｈｚ以下、好まし
くは沈積開始圧力以上、６００１ｍ Ｈ＆以下が望まし
く、温度が８００℃以上沈積開始温度以下、好ましくは
８５０℃以上沈積開始温度以下が望ましく、かつ、圧力
上昇または温度低下の少なくとも一方が実施されている
ことが必要である。At this time, the conditions from the start of carbon deposition to the end of the deposition are such that the pressure is above the deposition starting pressure and below 760 mm Hz, preferably above the deposition starting pressure and below 6001 mH&, and the temperature is preferably above 800°C and below the deposition starting temperature. It is desirable that the temperature is 850° C. or higher and lower than the deposition start temperature, and at least one of pressure increase and temperature decrease is required.
第１被膜の厚さは、目的に応じて任意に選択できるもの
であり、特に制限されないが、通常０１μ−〜５閣程度
が好ましい。The thickness of the first coating can be arbitrarily selected depending on the purpose and is not particularly limited, but it is usually preferably about 0.1μ to 5μ.
沈積に要する時間も、被膜の厚さに応じて任意にとり得
るものであり特に制限されないが、通常０１分〜１００
０時間程度が望ましい。The time required for deposition can also be taken arbitrarily depending on the thickness of the film and is not particularly limited, but it is usually 0.1 to 100 minutes.
Approximately 0 hours is desirable.
本発明にわいて、第２被膜は、第１被膜の上に気相熱分
解により形成される、セラミックスあるいはセラミック
スと炭素の再考から成る被膜である。気相分解によりセ
ラミックスあるいはセラミックスと炭素の再考から成る
ものを沈積する方法は通常ＣＶ Ｄ （Ｃｈｅｍｉｃａ
ｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）と呼ばれ、具
体的には熱ＣＶＤ、プラズマＣＶＤ等が挙げられる。In the present invention, the second coating is a coating made of ceramics or a combination of ceramics and carbon, which is formed on the first coating by vapor phase pyrolysis. The method of depositing ceramics or compositions of ceramics and carbon by vapor phase decomposition is usually CV D (Chemica
1 Vapor Deposition), and specific examples include thermal CVD and plasma CVD.
ＣＶＤにより炭素および／またはセラミックスを沈積す
る場合、セラミックスとしては、ＳｉＣ，ＺｒＣ，Ｔｉ
Ｃ，ＨｆＣ。When depositing carbon and/or ceramics by CVD, the ceramics include SiC, ZrC, Ti
C, HfC.
Ｂ、Ｃ，ＮｂＣ，ＷＣ，ＴｉＢ２．ＢＮあるいはＳｉ３
Ｎ、などがあげられ、中でもＳｉＣ，ＺｒＣ，ＴｉＣお
よびＨｆＣが好ましい。またこれらのセラミックスと炭
素とを同時に沈積させろこともできろ。B, C, NbC, WC, TiB2. BN or Si3
Among them, SiC, ZrC, TiC and HfC are preferred. It is also possible to deposit these ceramics and carbon simultaneously.
炭素を得るための熱分解ガスとしては炭化水素、好まし
くは炭素数１〜６の炭化水素、具体的には、メタン、天
然ガス、プロパン、ベンゼン等が用いられろ。またセラ
ミックスを得ろための熱分解ガスとしては、ハロゲン化
物、水素化物、有機金属化合物等あるいはこれらと前記
炭化水素ガスや水素、不活性ガスとの混合物が用いられ
る。具体的には、ＳＩＣには５ｉｃ１４．ＣＨ，５ｉＣ
１３，ＺｒＣにはＺｒＣｌ４． ＴｉＣにはＴＣ１４，
ＨｆＣにはＨｆＣ１，が使用できろ。As the pyrolysis gas for obtaining carbon, hydrocarbons, preferably hydrocarbons having 1 to 6 carbon atoms, specifically methane, natural gas, propane, benzene, etc. may be used. Further, as the pyrolysis gas for obtaining ceramics, halides, hydrides, organometallic compounds, etc., or mixtures of these with the above-mentioned hydrocarbon gases, hydrogen, and inert gases are used. Specifically, SIC has 5ic14. CH,5iC
13, ZrC contains ZrCl4. TC14 for TiC,
HfC1 can be used for HfC.
反応条件は、まず温度は８００〜２３００℃、好ましく
は１０００〜２０００℃、圧力は０５〜７ Ｂ ０ ｎ
ｎｉ Ｈｇ 、好ましくＩよ５０〜７ＢＯｍｍＨ１が望
ましい。The reaction conditions are: first, the temperature is 800 to 2300°C, preferably 1000 to 2000°C, and the pressure is 05 to 7 B 0 n
ni Hg, preferably 50 to 7 BOmmH1.
原料ガス供給速度は、反応に用いろ炉の大きさあるいは
構造によって適宜決定されろ。The raw material gas supply rate should be appropriately determined depending on the size or structure of the furnace used for the reaction.
沈積に要する時間は、第２被膜が所定の厚さになるまで
任意に実施できる。通常０．１分〜１００時間程度が望
ましい。The time required for the deposition can be set arbitrarily until the second coating reaches a predetermined thickness. Usually about 0.1 minute to 100 hours is desirable.
第２被膜の厚さは、目的に応じて任意に決定されるもの
であり特に制限されないが、通常０１μ１１１〜５而程
度であることが望ましい。The thickness of the second coating is arbitrarily determined depending on the purpose and is not particularly limited, but it is usually desirably about 01μ111 to 5μ.
実施例
以下に実施例をあげ、本発明を具体的に説明するが、本
発明はこれらに制限されるものではない。EXAMPLES The present invention will be specifically explained with reference to Examples below, but the present invention is not limited thereto.
（実施例１）
直径１０ミクロンのピッチ系炭素ｔａｌｆｉ２０００本
をＺ軸方向に、また同じ繊維４０００本をＸおよびＹ軸
方向に用いた直交３次元織物を強化繊維とし、石油ピッ
チをマトリックスの原料とする炭素／炭素複合材料の表
面に熱ＣＶＤにより平板方向の熱膨張係数が０．５ｘ
１０ （／℃）を有する炭素の被膜を合成し、また最
外層に熱膨張係数が４ Ｘ １０−’ （／’ｅ）を有
する炭素の被膜を合成して、その間の熱膨張係数を連続
的に変化させた。これを加熱炉中におき、前記第１被膜
の上に圧力５０Ｔｏｒｒ、原料ガス５ＩＣ１４＋ＣＨ４
＋Ｈ２、温度１４００℃の条件で熱ＣＶＤによりＳｉＣ
を沈積し第２被覆した。(Example 1) An orthogonal three-dimensional fabric using 2000 pitch-based carbon talfi fibers with a diameter of 10 microns in the Z-axis direction and 4000 same fibers in the X and Y-axis directions was used as the reinforcing fiber, and petroleum pitch was used as the raw material for the matrix. The thermal expansion coefficient in the flat direction is 0.5x by thermal CVD on the surface of the carbon/carbon composite material.
A carbon film with a thermal expansion coefficient of 4 x 10-'(/'e) was synthesized as the outermost layer, and the thermal expansion coefficient between them was continuously adjusted. changed to. This was placed in a heating furnace, and a pressure of 50 Torr was applied to the first coating, and a raw material gas of 5IC14+CH4
+H2, SiC by thermal CVD at a temperature of 1400℃
A second coating was applied.
得られたものを走査電子顕微鏡で観察したところ、炭素
／炭素複合材料の表佃にＣＶＤによる炭素が沈着してお
り、表面にｌｆ ＣＶ ｌ）によるＳｉＣの沈着がみら
れｔコ。When the obtained material was observed with a scanning electron microscope, it was found that carbon due to CVD was deposited on the surface of the carbon/carbon composite material, and SiC due to CVD was deposited on the surface.
炭素／炭素複合材料と第１被膜との界面、第１被膜内、
第２被膜内およびこれらの界面のいずれにおいてもクラ
ック、剥離などＩｉ認められなかった。The interface between the carbon/carbon composite material and the first coating, within the first coating,
No cracks, peeling, etc. were observed within the second coating or at any of these interfaces.
（実施例２）
直径１０ミクロンのピッチ系炭素ｍ維２０００本をＺ軸
方向に、また同じ繊維４０００本をＸおよびＹ軸方向に
用いた直交３次元織物を強化繊維とし、石油ピッチをマ
トリックスの原料とする炭素／炭素複合材料の表面に熱
ＣＶＤにより平板方向のヤング率が２７ Ｘ １０’ｋ
ｇｆ／ｍｍ２を有する炭素の被膜を合成し、また最外層
にヤング率が１． ＩＸ １０’ｋｇｆ／ｍｍ２を有す
る炭素の被膜を合成して、その間のヤング率を連続的に
変化させた。これを加熱炉中におき、前記第１被膜の上
に圧力５Ｔｏｒｒ、原料ガｙ、 ＣＨ，Ｓ ｉＣｌ、＋
Ｈ２、温度１３５０℃の条件で熱ＣＶＤによりＳｉＣ
を沈積し第２被覆した。(Example 2) An orthogonal three-dimensional fabric using 2000 pitch-based carbon fibers with a diameter of 10 microns in the Z-axis direction and 4000 of the same fibers in the X and Y-axis directions was used as the reinforcing fiber, and petroleum pitch was used as the matrix. The Young's modulus in the planar direction is 27 x 10'k by thermal CVD on the surface of the carbon/carbon composite material used as the raw material.
gf/mm2 was synthesized, and the outermost layer had a Young's modulus of 1. A carbon film having an IX of 10' kgf/mm2 was synthesized, and the Young's modulus was continuously varied therebetween. This was placed in a heating furnace, and the raw material gas, CH, SiCl, +
SiC by thermal CVD under the conditions of H2 and temperature 1350℃
A second coating was applied.
得られたものを走査電子顕微鏡で観察したところ、炭素
／炭素複合材料の表面にＣＶＤによる炭素が均一に沈着
しており、表面にはＣＶＤによる３ｉＣの沈着がみられ
た。炭素／炭素複合材料と第１被膜との界面、第１被膜
内、第２被膜内およびこれらの界面のいずれにおいても
クラック、剥離などは認められなかった。When the obtained material was observed with a scanning electron microscope, it was found that carbon by CVD was uniformly deposited on the surface of the carbon/carbon composite material, and 3iC was deposited on the surface by CVD. No cracks, peeling, etc. were observed at the interface between the carbon/carbon composite material and the first coating, within the first coating, within the second coating, or at any of these interfaces.
［発明の効果］
本発明の方法により得られる炭素材料は＃４酸化性に優
れろのみでなく、熱負荷条件下においてもクラックなど
の発生が起こり難く広範囲の用途が期待できる材料であ
る。[Effects of the Invention] The carbon material obtained by the method of the present invention not only has excellent #4 oxidation properties, but also is difficult to generate cracks even under heat load conditions, and is a material that can be expected to have a wide range of uses.
Claims (1)
なる第１被膜を気相分解により形成させ、ついでセラミ
ックスあるいはセラミックスと炭素の再考よりなる第２
被膜を気相分解により形成させ、かつ該第１被膜内にお
いて炭素の熱物性あるいは機械物性の少なくともひとつ
を連続的にあるいは非連続的に変化させていることを特
徴とする炭素材料の製造法。(1) Form a first film mainly made of carbon on the surface of the carbon/carbon composite material by vapor phase decomposition, and then form a second film made of ceramics or a reconsideration of ceramics and carbon.
1. A method for producing a carbon material, characterized in that a film is formed by vapor phase decomposition, and at least one of thermal and mechanical properties of carbon is changed continuously or discontinuously within the first film.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1192591A JP3007936B2 (en) | 1989-07-27 | 1989-07-27 | Manufacturing method of carbon material |
| US07/558,703 US5093156A (en) | 1989-07-27 | 1990-07-26 | Process for preparing carbon material |
| DE69007568T DE69007568T2 (en) | 1989-07-27 | 1990-07-27 | Process for the production of a carbon material. |
| EP90308252A EP0410781B1 (en) | 1989-07-27 | 1990-07-27 | Process for preparing carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1192591A JP3007936B2 (en) | 1989-07-27 | 1989-07-27 | Manufacturing method of carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0360413A true JPH0360413A (en) | 1991-03-15 |
| JP3007936B2 JP3007936B2 (en) | 2000-02-14 |
Family
ID=16293825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1192591A Expired - Lifetime JP3007936B2 (en) | 1989-07-27 | 1989-07-27 | Manufacturing method of carbon material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5093156A (en) |
| EP (1) | EP0410781B1 (en) |
| JP (1) | JP3007936B2 (en) |
| DE (1) | DE69007568T2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008019511A (en) * | 1995-04-07 | 2008-01-31 | Soc Natl Etud Constr Mot Aviat <Snecma> | Chemical vapor infiltration method with various infiltration parameters |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2654094B1 (en) * | 1989-11-09 | 1993-07-09 | Aerospatiale | PROCESS FOR THE MANUFACTURE OF A CARBON MATERIAL PROTECTED AGAINST OXIDATION BY ALUMINUM NITRIDE AND MATERIAL OBTAINED BY THIS PROCESS. |
| US5523035A (en) * | 1989-11-15 | 1996-06-04 | Nippon Oil Co., Ltd. | Process for producing carbonaceous material |
| JPH03199172A (en) * | 1989-12-27 | 1991-08-30 | Sumitomo Electric Ind Ltd | Coated carbon fiber reinforced composite material |
| FR2668477B1 (en) * | 1990-10-26 | 1993-10-22 | Propulsion Ste Europeenne | REFRACTORY COMPOSITE MATERIAL PROTECTED AGAINST CORROSION, AND METHOD FOR THE PRODUCTION THEREOF. |
| FR2678955B1 (en) * | 1991-07-12 | 1994-04-15 | Applications Couches Minces | SUBSTRATE COATED WITH A THIN LAYER BASED ON CARBON AND SILICON, ITS PREPARATION AND ITS USE. |
| US5288438A (en) * | 1991-11-22 | 1994-02-22 | The Aerospace Corporation | Carborane catalyzed graphitization of polyarylacetylene (PAA) |
| US5837081A (en) * | 1993-04-07 | 1998-11-17 | Applied Sciences, Inc. | Method for making a carbon-carbon composite |
| US5690997A (en) * | 1993-10-04 | 1997-11-25 | Sioux Manufacturing Corporation | Catalytic carbon--carbon deposition process |
| US5803210A (en) * | 1994-12-28 | 1998-09-08 | Nippon Oil Co., Ltd. | Disk brakes |
| US20040122515A1 (en) * | 2002-11-21 | 2004-06-24 | Xi Chu | Prosthetic valves and methods of manufacturing |
| US7947372B2 (en) | 2005-08-18 | 2011-05-24 | Sulzer Metaplas Gmbh | Substrate coated with a layered structure comprising a tetrahedral carbon layer and a softer outer layer |
| US20090061085A1 (en) * | 2007-09-04 | 2009-03-05 | Honeywell International Inc. | Expedited manufacture of carbon-carbon composite brake discs |
| CN102296355B (en) * | 2011-06-27 | 2013-12-11 | 湖南金博复合材料科技有限公司 | Guide shell made from carbon/carbon composite material and production method |
| RU2675618C1 (en) * | 2017-12-27 | 2018-12-20 | Акционерное общество "Государственный Ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (АО "ГНИИХТЭОС") | Method of applying oxidation-resistant and ultra-high-temperature titanium, zirconium and hafnium diboride coatings to composite materials |
| CN111285703B (en) * | 2020-03-31 | 2022-05-10 | 西安超码科技有限公司 | Method for manufacturing low-cost double-element carbon matrix airplane carbon brake disc |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3385723A (en) * | 1964-06-26 | 1968-05-28 | Martin Marietta Corp | Carbon article coated with beta silicon carbide |
| US4397901A (en) * | 1979-07-31 | 1983-08-09 | Warren James W | Composite article and method of making same |
| US4405685A (en) * | 1980-11-13 | 1983-09-20 | Agency Of Industrial Science & Technology, Ministry Of International Trade & Industry | Carbon fibers with duplex metal carbide coating and methods for manufacture thereof |
| US4472476A (en) * | 1982-06-24 | 1984-09-18 | United Technologies Corporation | Composite silicon carbide/silicon nitride coatings for carbon-carbon materials |
| US4487799A (en) * | 1982-06-24 | 1984-12-11 | United Technologies Corporation | Pyrolytic graphite pretreatment for carbon-carbon composites |
| US4766013A (en) * | 1983-03-15 | 1988-08-23 | Refractory Composites, Inc. | Carbon composite article and method of making same |
| GB2161151B (en) * | 1984-07-04 | 1988-03-02 | United Technologies Corp | Composite sic/si3n4 coatings for carbon-carbon materials |
| JPS6479071A (en) * | 1987-09-22 | 1989-03-24 | Petoca Ltd | Production of high strength carbon-carbon composite material |
-
1989
- 1989-07-27 JP JP1192591A patent/JP3007936B2/en not_active Expired - Lifetime
-
1990
- 1990-07-26 US US07/558,703 patent/US5093156A/en not_active Expired - Fee Related
- 1990-07-27 DE DE69007568T patent/DE69007568T2/en not_active Expired - Fee Related
- 1990-07-27 EP EP90308252A patent/EP0410781B1/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008019511A (en) * | 1995-04-07 | 2008-01-31 | Soc Natl Etud Constr Mot Aviat <Snecma> | Chemical vapor infiltration method with various infiltration parameters |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69007568T2 (en) | 1994-06-30 |
| US5093156A (en) | 1992-03-03 |
| EP0410781B1 (en) | 1994-03-23 |
| DE69007568D1 (en) | 1994-04-28 |
| JP3007936B2 (en) | 2000-02-14 |
| EP0410781A1 (en) | 1991-01-30 |
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